In this study, the effects of organoclay loading, compatibilizer loading and polyethylene type on the morphology, rheology, thermal properties and mechanical properties of polyethylene/compatibilizer/organoclay nanocomposites were investigated. As compatibilizer, terpolymer of ethylene-methacrylate-glycidyl methacrylate (Lotader&reg / AX8900), as organoclay Cloisite&reg / 15A were used. All samples were prepared by a co-rotating twin screw extruder, followed by injection molding. Considering ternary nanocomposites, highest impact strength results were obtained with 10% compatibilizer plus 2% organoclay / highest yield stress, elastic modulus, flexural strength, flexural modulus were obtained with 5% compatibilizer plus 4-6% organoclay. DSC data indicated that addition of organoclay and compatibilizer did not change the melting point remarkably / on the other hand it affected the crystallinity. The organoclay used had no nucleation effect on polyethylene, and the compatibilizer decreased the crystallinity of the matrix. X-ray diffraction showed that in all ternary nanocomposites and in binary nanocomposite of high density polyethylene with organoclay, layer separation associated with intercalation of the clay structure occurred,. The highest increase of interlayer gallery spacing was obtained with 10% compatibilizer plus 2% organoclay, which were 25%, 28% and 27% for HDPE, LLDPE and LDPE matrices respectively.

The present study was aimed at exploring the purification and modification of montmorillonite rich Turkish bentonites by organic salts and their subsequent effects on the morphology (X-diffractometry, transmission electron microscopy, scanning electron microscopy), melt flow index, mechanical (Tensile, Impact) and especially thermal stability (thermal gravimetric analysis, differential scanning calorimetry) properties of polymer/organoclay nanocomposites with and without an elastomeric compatibilizer. The bentonite clay mined from Resadiye (Tokat/Turkey) was purified by sedimentation, resulting in higher cation exchange capacity and thermal stability in comparison to unpurified clay, and then used in the synthesis of six thermally stable organoclays by replacing the interlayer inorganic sodium cations with two (alkyl, aryl) phosphonium and four di-(alkyl, aryl) imidazolium surfactant cations in an attempt to overcome the problem of early decomposition of alkyl ammonium organoclays usually used in polymer nanocomposites. An optimum amount of these organoclays (wt %2) was then used in the production of Polyamide 66 and Poly(ethylene terephthalate) based nanocomposites by melt blending with the help of an optimum amount of elastomeric compatibilizer (wt %5) which also acted as impact modifier. Phosphonium organoclays were used in the production of nanocomposites for both polymers, whereas imidazolium organoclays were used with PET only. The importance of clay purification was revealed in the removal of non-clay minerals available in the raw bentonite clay as confirmed by XRF and XRD, the significant increase in cation exchange capacity and the improved thermal stability of the purified clays as proven by TGA. The interlayer spacing of the phosphonium organoclays ranged from 1.78 to 2.52 nm indicating arrangement between pseudo-trilayers and paraffin-type chains, while the interlayer spacing of imidazolium organoclays ranged between 1.35 nm and 1.45 nm indicating a monolayer arrangement. The effects of chemical structure (chain type), counter ion and alkyl chain length on the thermal stability of the imidazolium salts were investigated. TGA analysis showed that the thermal stability of (alkyl, aryl) phosphonium and di-(alkyl, aryl) imidazolium organoclays proved to be superior to conventionally used quaternary alkyl ammonium organoclays. Not only the thermal stability of the organoclays prevented the nanocomposite from early decomposition, but these organoclays also improved the onset decomposition temperatures of PA66 and PET nanocomposites compared to the pure polymer owing to the dominant barrier effect of the silicate layers as a result of the formation of carbonaceous-silicate char. The reinforcement of PA66 with surface modified phosphonium organoclays and PET with surface modified phosphonium and imidazolium organoclays enhanced the mechanical and thermal properties of the binary and ternary nanocomposites. The mechanical properties were in good agreement with DSC analysis for all the PA66 and PET compositions. The presence of elastomer and organoclays promoted the nucleation process in PA66 blend, binary and ternary nanocomposites. However, the presence of elastomer and organoclay retarded the nucleation in most of the PET composites.

<p>U ovom radu, sintetisani su poli(uretan-izocijanuratni) elastomeri sa kovalentnim<br />čvorovima, katalitičkom ciklotrimerizacijom teleheličnih diizocijanata kao prekursora mreže<br />na osnovu 2,4-toluen-diizocijanata, &alpha;,&omega;-dihidroksipoli(oksipropilen)diola i monoola<br />dietilenglikolmonometiletra. Dobijeni su i termoplastični segmentirani poliuretani, sa<br />čvorovima fizičkog umreženja, jednostepenim postupkom i metodom prepolimerizacije,<br />reakcijom dve vrste alifatskog polikarbonatnog diola, koji se razlikuju u strukturi lanca,<br />heksametilen-diizocijanata i produživača lanca (1,4-butandiola). Sintetisana je i serija<br />poliuretanskih hibridnih materijala, dodatkom 1% <em>m/m</em> nanočestica organski modifikovanih<br />glina (montmorilonita i bentonita). Prioritet rada je bio da se utvrdi uticaj udela elastično<br />aktivnih i visećih lanaca na dinamičko-mehanička svojstva, toplotnu stabilnost i svojstva<br />prigu&scaron;enja poliuretanskih mreža sa izocijanurat (heksahidro-1,3,5-triazin-2,4,6-trion)<br />prstenovima, kao čvorovima. Takođe, cilj istraživanja je bio da se ispita uticaj odnosa<br />reaktivnih grupa diizocijanata, polikarbonatne komponente i produživača lanca, kao i dodatka nanočestica na svojstva povr&scaron;ine, morfologiju, dinamičko-mehanička i toplotna svojstva segmentiranih neojačanih i ojačanih elastomera. Toplotna degradacija poli(uretanizocijanuratnih) mreža i segmentiranih termoplastičnih poliuretana praćena je neizotermskim ispitivanjima, koristeći istovremenu termogravimetrijsku i masenu analizu (TG-MS), kao i istovremenu termogravimetriju i diferencijalno skenirajuću kalorimetriju (TG-DSC). Viskoelastična svojstva i svojstva prigu&scaron;enja dobijenih poliuretanskih elastomera su ispitivana pomoću dinamičko-mehaničke analize (DMA). Toplotno pona&scaron;anje segmentiranih poliuretana i nanokompozita, dobijenih jednostepenim postupkom sinteze, je proučavano modulovanom diferencijalno skenirajućom kalorimetrijom (MDSC). Temperatura prelaska u staklasto stanje i termoplastična svojstva neojačanih i ojačanih poliuretanskih materijala, dobijenih postupkom prepolimerizacije, određeni su primenom diferencijalno skenirajuće kalorimetrije (DSC). Hemijska struktura i formiranje vodoničnih veza dobijenih elastomera proučavane su koristeći Furijeovu transmisionu infracrvenu spektroskopiju (FTIR). Uticaj udela tvrdih segmenata na morfologiju i svojstva povr&scaron;ine segmentiranih poliuretana, ispitivan je pomoću mikroskopije atomskih sila (AFM). Stepen kristalnosti uzoraka i dispergovanje nanočestica u dobijenim hibridnim materijalima su odre&ntilde;eni primenom metode rasipanja X-zraka pod &scaron;irokim uglom (WAXS).</p> / <p> In this work, poly(urethane-isocyanurate) elastomers, with covalent junction points,<br /> were synthesized by catalytic cyclotrimerization of telechelic diisocyanates as network<br /> presursors based on 2.4-tolylenediisocyanate, a,w,dihydroxypoly(oxypropylene) and monool<br /> component 2-(2-metoxyetoxy)ethanol. Thermoplastic polyurethanes, with physical<br /> crosslinking, were obtained by one-step technique and pre-polimerization method, using two<br /> aliphatic polycarbonate diols (differening in chain constitution), hexamethylene-diisocyanate<br /> and chain extender (1,4-butane diol) as reactive components. One serie of polyurethane<br /> hybrid materials was prepared by addition of 1 wt. % of organically modified clay<br /> nanoparticles (bentonite and montmorillonite). The goal of this work was to investigate the<br /> influence of elastically active and dangling chains content on thermal stability, dynamic<br /> mechanical and damping properties of polyurethane networks with heat-resistant<br /> isocyanurate-(hexahydro-1,3,5-triazin-2,4,6-trion) rings, as crosslinks. The aim was also to<br /> determine the influence of diisocyanate, macrodiol and chain extender reactive groups&rsquo; ratio<br /> and nanoparticles addition on surface properties, morphology, dynamic mechanical and<br /> thermal properties of obtained segmented unfilled and filled elastomers. Thermal degradation<br /> of poly(urethane-isocyanurate) networks and segmented thermoplastic polycarbonate-based<br /> polyurethanes was investigated by nonisothermal analysis, using thermogravimetry coupled<br /> with mass spectroscopy analysis (TG-MS) and thermogravimetry coupled with differential<br /> scanning calorimetry (TG-DSC). Viscoelastic and damping properties of obtained<br /> polyurethane elastomers were estimated by dynamic mechanical measurements (DMA).<br /> Modulated differential calorimetry (MDSC) was used to investigate thermal behavior of<br /> segmented polyurethanes and nanocomposites, synthesized using one-step technique. The<br /> glass transition temperature and thermoplastic properties of unfilled and filled polyurethane<br /> materials, prepared by pre-polimerization procedure were assessed by differential scanning<br /> calorimetry (DSC). Fourier transform infrared spectroscopy (FTIR) was used to investigate<br /> the hydrogen bond formation and chemical structure of prepared segmented elastomers. The<br /> investigation of the influence of hard segment content on morphology and surface topography<br /> of prepared segmented elastomers sheets was done by atomic force microscope (AFM). In<br /> order to determine the degree of cristallinity and to evaluate the dispersion of<br /> montmorillonite and bentonite in the polyurethane matrices, the prepared hybrid materials<br /> were characterized by wide angle X-ray scattering (WAXS).</p>

Made available in DSpace on 2016-12-08T17:19:27Z (GMT). No. of bitstreams: 1 Samara Bohn.pdf: 2670870 bytes, checksum: 4b9de8d71921764eee1942da211fad27 (MD5) Previous issue date: 2015-09-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The poly (vinyl chloride) (PVC) is one of thermoplastic polymers most consumed worldwide, because it has a broad scope and can be used from rigid pipes and profiles up toys and extremely flexible films obtained with the addition of plasticizers. The addition of nanofillers in polymer matrices has aroused the interest of many researchers seeking to improve properties of materiais and reduce the cost of producing them. In this work, the objective was to evaluate the effect of plasticizer in the nanoclays dispersion in the polymer matrix of poly (vinyl chloride) (PVC). Three different plasticizers ware used, one being the family of phthalate (dioctyl phthalate DOP), on the family of adipate (dioctyl adipate DOA) and the third, called by some green plasticizers poly (e-caprolactone) PCL. Furthermore, it was also evaluated the effect of clay pre-dispersion in the plasticizer in the properties of the nanocomposites. The samples were prepared in single screw extruder and characterized by means of scanning electron field effect (SEM FEG) and transmission electron microscopy (TEM), diffraction X-ray (XRD), differential scanning calorimetry (DSC) tensile and swelling test. The morphology shows a heterogeneous distribution in the matrix, since phase separation, ocorred and clay agglomerates. However it was found that the use of the pre-dispersion can reduce the agglomerates and form small regions interleaving and further reduce the size of the phases, and found that even if different plasticizers would provide different results. By DRX it was found that the inclusion of clay pre-dispersed by sonication on the matrix promotes increased crytallinity of 75% compared with the sample without DOP clay, other samples had smaller increases. In differential scanning calorimetry it was observed over a Tg heterogeneity in the plasticization of PVC. In tensile teste it was found that inclusion of clay plasticized PVC promoted 5% and 10% in Young s modulus for PVC/DOP samples with sonification and PVC/PCL respectively with magnetic stirring. While the samples decreased with DOA Young s modulus within 19%, and the samples were also had smaller reduction in the migration of the plasticizer during the swelling test. According to the results found was that the clay pre-dispersion in theplasticizer may facilitate intercalation of the some but dosen t eliminate large amounts of agglomerates in the nanocomposity which can have great influence on the properties mechanical, thermal and migration, and the type of palsticizer has a remarkable effect on the nanocomposite. / O poli (cloreto de vinila) (PVC) é um dos polímeros termoplásticos mais consumidos mundialmente, pois o mesmo tem um vasto campo de aplicação podendo ser utilizado desde tubos e perfis rígidos até brinquedos e filmes extremamente flexíveis obtidos com a adição de plastificantes. A adição de nanocargas em matrizes poliméricas tem despertado interesse de muitos pesquisadores, que buscam melhorar propriedades dos materiais e reduzir o custo de produção dos mesmos. Neste trabalho, o objetivo foi avaliar o efeito do plastificante na dispersão de nanoargilas em matriz polimérica de poli (cloreto de vinila) (PVC). Foram utilizados três diferentes plastificantes, sendo um deles da família dos ftalatos (dioctil ftalato - DOP), um da família dos adipatos (dioctil adipato - DOA) e o terceiro, chamado por alguns de plastificante verde poli (&#949;-caprolactona) PCL. Além disso, também foi avaliado o efeito da pré-dispersão da argila nos plastificantes nas propriedades dos nanocompósitos. As amostras foram preparadas em extrusora monorosca e caracterizadas por meio de microscopia eletrônica de varredura de efeito de campo (MEV-FEG) e microscopia eletrônica de transmissão (MET), difração de raios-X (DRX), calorimetria exploratória diferencial (DSC), ensaios de tração e ensaio de intumescimento. A morfologia apresentou uma distribuição heterogênea na matriz, pois ocorreu separação de fase e aglomerados de argila. No entanto, verificou-se que a utilização da pré dispersão pode reduzir os aglomerados e formar pequenas regiões de intercalação, e ainda reduzir o tamanho das fases, e ainda constatou-se que diferentes plastificantes promovem resultados diferentes. Por meio de DRX constatou-se que a inserção de argila pré-dispersa por sonicação na matriz promove aumento de 75% na cristalinidade em relação a amostra com DOP sem argila, as demais amostras tiveram aumento menores. Na calorimetria exploratória diferencial foi observado mais de uma Tg indicando heterogeneidade na plastificação do PVC. Nos ensaios de tração foi verificado que a inserção de argila no PVC plastificado promoveu aumentos de 5% e 10% no módulo de Young para as amostras PVC/DOP com sonicação e PVC/PCL com agitação magnética, respectivamente. Enquanto que as amostras com DOA apresentaram redução do módulo de Young em até 19%, e também foram as amostras que tiveram a menor redução na migração do plastificante durante os ensaios de intumescimento. De acordo com os resultados foi verificado que a pré-dispersão da argila no plastificante pode facilitar a intercalação da mesma, mas não elimina a grande quantidade de aglomerados nos nanocompósitos o que pode ter grande influência sobre as propriedades mecânicas, térmicas e de migração, bem como o tipo de plastificante influencia de forma considerável sobre os nanocompósitos.

En Afrique sud- saharienne, plusieurs méthodes de protection des stocks alimentaires sont utilisées ; parmi elles, les insecticides synthétiques qui représentent un risque réel pour la santé humaine. Pour apporter une alternative à ces insecticides chimiques potentiellement dangereux, le présent travail a pour objectif de développer des bio-insecticides en formulant des poudres par adsorption d’huiles essentielles sur des argiles. Deux argiles naturelles du Cameroun ont été utilisées comme adsorbants des composés terpéniques des huiles essentielles de Xylopia aethiopica et Ocimum gratissimum pour la préparation d’insecticides. Dans le but d’améliorer leur capacité d’adsorption, ces argiles ont été traitées par la soude et l’acide sulfurique. Elles ont également été modifiées par des solutions de polycations d’aluminium ou de fer de rapport molaire varié ainsi que par des cations d’alkylammoniums. Une bentonite commerciale a été utilisée comme référence dans le suivi des modifications. Ces différentes matrices ont été caractérisées avant et après modifications par diffraction des rayons X, adsorption-désorption d’azote, spectroscopie infra rouge à transformée de Fourier, analyses thermogravimétriques et différentielles, et photométrie de flamme. Il ressort de la caractérisation que l’échantillon de Wak est majoritairement constitué de kaolinite, et celui de Maroua de montmorillonite. Le traitement par l’acide sulfurique et par les polycations métalliques entraînent une augmentation de la surface spécifique des argiles, tandis que la soude et les cations d’alkylammoniums la réduisent fortement. La surface spécifique de la montmorillonite passe de 82 m².g-1 à 4,5 m².g-1 après traitement au céthyl triméthyl ammonium (CTMA). Les diffractogrammes montrent une augmentation de la distance interfoliaire des argiles étudiées après modification aux cations alkylammoniums. La distance interfoliaire augmente de 5,5 Å et de 10,6 Å respectivement pour la montmorillonite et la bentonite traitée par le CTMA. Les argiles de type smectite après modifications aux polycations métalliques, présentent en revanche un étalement du pic caractéristique de l’espace interfoliaire. Les cations alkylammoniums entraînent donc une intercalation effective des molécules de CTMA et phényl triméthyl ammonium (PTMA) entre les feuillets de montmorillonite et de bentonite tandis que les polycations métalliques entraînent une exfoliation du matériau argileux. Les argiles-alkylammoniums présentent les plus grandes capacités d’adsorption des composés terpéniques malgré les plus faibles surfaces spécifiques. Ainsi, face aux composés terpéniques, la capacité d’adsorption des argiles ne dépend pas uniquement de la surface spécifique mais également de l’espacement interfoliaire de l’adsorbant ainsi que de l’affinité des molécules d’adsorbât vis-à-vis de l’adsorbant. Des tests insecticides ont montré que les formulations à base de la Mont-CTMA présentent une toxicité plus stable que celle préparée à partir de l’argile brute (Mont-Na). La formulation Mont-Na-HE perd la totalité de son activité insecticide au bout de 30 jours de conservation dans les boîtes ouvertes. La formulation Mont-CTMA-HE par contre n’en perd qu’environ 60% dans les mêmes conditions. La rémanence de la formulation varie avec l’adsorbant utilisé ; car l’effet insecticide de l’huile essentielle d’O. gratissimum persiste pendant 107 jours lorsqu’elle est fixée sur la Mont-CTMA, tandis que fixée sur l’argile brute, elle perd son activité au bout de 45 jours. Ces résultats nous permettent d’affirmer que les argiles modifiées augmentent la durée de l’effet insecticide des huiles essentielles et peuvent être utilisées pour une application industrielle dans la production des bio-insecticides. / In sub-Saharan Africa, several methods to protect food stocks are used ; amongst them are synthetic insecticides. These synthetic insecticides pose high real risk to human health. This study aims at providing an alternative to the dangerous synthetic chemical insecticides, by developing bioinsecticides formulating powders through adsorption of essential oils on Cameroonian clays. Two natural clays collected in Cameroon were used as adsorbents of terpene compounds of Xylopia aethiopica and Ocimum gratissimum essential oils, for the preparation of insecticides. The clay fractions were obtained from soil aggregates by sedimentation. In order to improve their adsorption capacity, these clays were treated with sodium hydroxide and sulfuric acid. They were also modified with solutions of aluminum, iron polycations with molar ratio varied and alkylammoniums cations. A commercial bentonite was used as reference for these modifications. These different adsorbents materials were characterized before and after modifications by X-ray diffraction, nitrogen adsorption-desorption, infrared Fourier transform spectroscopy, thermal analysis, and flame photometry. According to the characterizations of the clay materials, Wak sample contained more kaolinite clay, while Maroua sample contained more montmorillonite clay. The sulfuric acid and metallic polycations caused an increase in the specific surface of clays, while sodium hydroxyl and alkylammoniums cations greatly reduced the SBET. For example, the Mont-Na+ SBET decreased from 82 m². g-1 to 4.5 m².g-1 after treatment with cetyl trimethyl ammonium (CTMA). Diffractogrammes showed spacing of smectites interlayer (montmorillonite and bentonite) after treatments with alkylammoniums cations at 5.5 Å and 10.6 Å respectively, for the interlayer space of Mont- CTMA and Bentonite- CTMA clays. After treatments with metallics polycations, smectite clays show a broadening of characteristic peak. Alkylammoniums cations led to an effective insertion of CTMA molecules and phenyl trimethyl ammonium (PTMA) between the interfoliar space of montmorillonite and bentonite while the metal polycations led to an exfoliation of the same clays. The interreticular spacings of kaolinite remain unchanged after any treatments. The kinetic model of pseudo second order is applicable to the adsorption of terpenic compounds by clays. Finding also showed that spread is not the only limiting factor in the process of adsorption of terpene compounds. Alkylammoniums-clays have the largest adsorption capacities of terpene compounds despite the lower specific surface they present. All this allows us to maintain that in the presence of terpenic compounds, the adsorption capacity of clays depends not only on the SBET but more on the interlayer spacing of the adsorbent and on the affinity of the adsorbate molecules toward the adsorbent. Concerning bioassays, it appears that the formulations made with Mont- CTMA presented a more stable toxicity than Mont-Na. Mont-Na-EO formulation loses all its insecticidal activity after 30 days of storage in the open boxes ; while Mont-CTMA- EO formulation only loses about 60% under the same conditions. Moreover, the Mont-Na-EO loses 50% of its insecticidal power (LD50) after 6 days ; while Mont-CTMA- EO loses the same quantity after 16 days when stored in open boxes. The remnance effect of the formulations based on essential oil varied with the adsorbent used. Because the insecticidal effect of O. gratissimum essential oil persisted during 107 days when it is adsorbed on Mont-CTMA, when adsorbed on Mont-Na, it loses all its activity for about 45 days. These results allow us to assert that modified clays increase the duration of the insecticidal effect of essential oils and can be used for industrial application in the production of bio-insecticides based on essential oils.

<p>Cilj&nbsp; ovog&nbsp; rada&nbsp; bio&nbsp; je&nbsp; ispitivanje&nbsp; mogućnosti&nbsp; primene&nbsp; modifikovanog&nbsp; bentonita&nbsp; kao katalizatora&nbsp; (ferioksalat&nbsp; i&nbsp; Al,&nbsp; Fe-bentonit&nbsp; katalizatori)&nbsp; u&nbsp; Fenton&nbsp; i&nbsp; foto-Fenton&nbsp; procesu&nbsp; uklanjanja tekstilne&nbsp; reaktivne&nbsp; boje&nbsp; Reactive&nbsp; Red&nbsp; 120.&nbsp; Do&nbsp; sada&nbsp; su&nbsp; objavljene&nbsp; studije&nbsp; primene&nbsp; heterogenog Fenton procesa sa različitim koncentracijama gvožđau katalizatorima i sa kompleksom ferioksalata,međutim, njihovo poređenje u smislu efikasnosti obezbojavanja nije istraženo, &scaron;to je bio jedan od fokusa&nbsp; istraživanja&nbsp; u&nbsp; ovom&nbsp; radu.&nbsp; Osim&nbsp; toga,&nbsp; potencijal&nbsp; sunčeve&nbsp; energije&nbsp; predstavlja&nbsp; 16,7%&nbsp; od ukupno&nbsp; iskoristivog&nbsp; potencijala&nbsp; obnovljivih&nbsp; izvora&nbsp; energije&nbsp; u&nbsp; Srbiji,&nbsp; dok&nbsp; je&nbsp; prosečno&nbsp; sunčevo zračenje&nbsp; u&nbsp; Srbiji&nbsp; oko&nbsp; 40%&nbsp; vi&scaron;e&nbsp; od&nbsp; evropskog&nbsp; proseka,&nbsp; čineći&nbsp; ga&nbsp; vrlo&nbsp; zanimljivim&nbsp; za&nbsp; primenu&nbsp; u ovom tipu tretmana. U cilju &scaron;to boljeg iskori&scaron;ćenjasunčevog zračenja i unapređenja fotokatalitičkih performansi&nbsp; procesa&nbsp; primenjen&nbsp; je&nbsp; parabolični&nbsp; koncentri&scaron;ući&nbsp; reaktor,&nbsp; koji&nbsp; je&nbsp; za&nbsp; ovu&nbsp; vrstu&nbsp; procesa prvi put upotrebljavan. Proučavano je u kojoj meri je solarna fotokataliza značajan segment tehnike za tretman otpadnih voda tokom degradacije perzistentnih jedinjenja, kao &scaron;to je organska azo boja. Takođe, utvrđen je i potencijal fotolize vodonik-peroksida za obezbojavanjem sintetičkog rastvora date&nbsp; boje.&nbsp; Prva&nbsp; faza&nbsp; imala&nbsp; je&nbsp; za&nbsp; cilj&nbsp; sintezu&nbsp; materijala&nbsp; primenom&nbsp; različitih&nbsp; metoda&nbsp; pripreme&nbsp; i<br />konstrukciju solarnog paraboličnog reaktora, koji će se koristiti u Fenton i foto-Fenton procesima degradacije boje Reactive Red 120. Druga faza je podrazumevala karakterizaciju novosintetisanih materijala i optimizaciju procesa fotokatalize primenom Fenton i foto-Fenton procesa i određivanje postignutih efikasnosti primenjenih procesa. Takođe, vr&scaron;eno je određivanje stepena mineralizacije i identifikacija degradacionih produkata nakon procesa degradacije tekstilne boje Reactive Red 120, kao&nbsp; i&nbsp; primena&nbsp; foto-Fenton&nbsp; procesa&nbsp; na&nbsp; realnom&nbsp; efluentu.&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; tokom primene Fenton procesa i kori&scaron;ćenjem oba tipa katalizatora u periodima niskog i visokog intenziteta zračenja,&nbsp; sa&nbsp; aspekta&nbsp; postizanja&nbsp; visoke&nbsp; efikasnosti&nbsp; obezbojavanja&nbsp; i&nbsp; najmanjeg&nbsp; izluživanja&nbsp; gvožđa,<br />može&nbsp; se&nbsp; zaključiti&nbsp; da&nbsp; je&nbsp; Fenton&nbsp; proces&nbsp; najefikasniji&nbsp; na&nbsp; pH&nbsp; vrednosti&nbsp; 3.&nbsp; AlFeB&nbsp; je&nbsp; pokazao&nbsp; veću reaktivnost čak i pri manje upotrebljenim dozama od0,05 g u odnosu na CuOFeB (0,2 g), kao i mogućnost&nbsp; manje&nbsp; upotrebe&nbsp; vodonik-peroksida&nbsp; od&nbsp; 2,5&nbsp; mM,&nbsp; za&nbsp; postizanje&nbsp; visoke&nbsp; efikasnosti obezbojavanja i postignut visok stepen mineralizacije. Vi&scaron;i intenzitet sunčevog zračenja omogućava odvijanje reakcije obezbojavanja na vi&scaron;im pH vrednostima primenom oba katalizatora tokom fotoFenton&nbsp; procesa.&nbsp; Ovo&nbsp; je&nbsp; posebno&nbsp; izraženo&nbsp; kod&nbsp; CuOFeB&nbsp; tokom&nbsp; letnjeg&nbsp; perioda&nbsp; (pH&nbsp; 7),&nbsp; čak&nbsp; i&nbsp; pri nižim dozama katalizatora. Međutim, najveći udeo u&nbsp; procesu obezbojavanja pri upotrebi CuOFeB katalizatora ima fotoliza vodonik-peroksida (80%). Suprotno ovim rezultatima, pri istim reakcionim uslovima,&nbsp; potrebna&nbsp; je&nbsp; veća&nbsp; količina&nbsp; AlFeB&nbsp; katalizatora&nbsp; (0,1&nbsp; g)&nbsp; i&nbsp; niža&nbsp; pH&nbsp; vrednost&nbsp; reakcije,&nbsp; a efikasnost&nbsp; procesa&nbsp; značajno&nbsp; zavisi&nbsp; od&nbsp; početne&nbsp; koncentracije&nbsp; H₂O₂.&nbsp; Činjenica&nbsp; da&nbsp; se&nbsp; u&nbsp; pripremi katalizatora koristio bentonit kao prirodan, &scaron;irokorasprostranjen i jeftin materijal i solarno zračenje kao obnovljiv i alternativni izvor fotona, gore navedene rezultate bi trebalo uzeti u obzir prilikom analize tro&scaron;kova efikasnosti primenjenog procesa. Takođe, primena unapređenih procesa oksidacije se&nbsp; razmatra&nbsp; kao&nbsp; predlog&nbsp; za&nbsp; najbolju&nbsp; dostupnu&nbsp; tehniku&nbsp; kada&nbsp; je&nbsp; u&nbsp; pitanju&nbsp; tretman&nbsp; otpadne&nbsp; vode tekstilne industrije, dok se kao dodatne nove tehnike uzimaju u obzir foto-oksidacije i ispitivanje mogućnosti&nbsp; njihove&nbsp; primene&nbsp; u&nbsp; preči&scaron;ćavanju&nbsp; otpadne&nbsp; vode&nbsp; u&nbsp; tercijarnom&nbsp; tretmanu&nbsp; na poluindustrijskim sistemima.<br />&nbsp;</p> / <p>The aim of this study was to investigate the decolorization efficiency of Reactive Red 120&nbsp; (RR120) synthetic solution using ferrioxalate (CuOFeB) and Al, Fe-bentonite (AlFeB) catalysts in&nbsp; Fenton&nbsp; and&nbsp; photo-Fenton&nbsp; process.&nbsp; So&nbsp; far,&nbsp; studies&nbsp; of the&nbsp; application&nbsp; of&nbsp; a&nbsp; solar-assisted&nbsp; heterogeneous Fenton process with various Fe loaded catalysts and with ferrioxalate complex have&nbsp; been published, but according to&nbsp;&nbsp; the author&rsquo;s knowledge, their comparison in terms of efficacy of&nbsp; decolorization&nbsp; has&nbsp; not&nbsp; been&nbsp; performed,&nbsp; which&nbsp; was&nbsp; one&nbsp; of&nbsp; the&nbsp; focus&nbsp; of&nbsp; research&nbsp; in&nbsp; this&nbsp; paper.&nbsp; In addition, the potential of solar energy represents&nbsp; 16.7% of the total utilized&nbsp; potential of renewable&nbsp; energy sources in Serbia, while the average solar radiation in&nbsp; Serbia is&nbsp; about 40% higher than the&nbsp; European average, making it very interesting for&nbsp; application in this type of treatment. In order to&nbsp; optimize the use of solar radiation and to improve&nbsp; the photocatalytic performance of the process, parabolic&nbsp; concentrating&nbsp; reactor&nbsp; was&nbsp; used&nbsp; for&nbsp; the&nbsp; first&nbsp; time.&nbsp; As&nbsp; a&nbsp; significant&nbsp; segment&nbsp; of&nbsp; the&nbsp; wastewater&nbsp; treatment&nbsp; technique&nbsp; during&nbsp; the&nbsp; degradation&nbsp; of&nbsp; persistent&nbsp; compounds,&nbsp; such&nbsp; as&nbsp; organic azo dye, solar photocatalysis was studied. Also, the potential of photolysis of hydrogen peroxide for&nbsp; decolorization of the synthetic dye solution was determined. Aim of the first phase of the study was synthesizing&nbsp; materials&nbsp; by&nbsp; using&nbsp; different&nbsp; methods&nbsp; of&nbsp; preparation,&nbsp; and&nbsp; construction&nbsp; of&nbsp; a&nbsp; solar&nbsp; parabolic reactor, which will be used in Fenton andphoto-Fenton dye degradation processes. The second phase involved the characterization of newlysynthesized materials and the optimization of the&nbsp; photocatalytic&nbsp; process&nbsp; by&nbsp; applying&nbsp; Fenton&nbsp; and&nbsp; photo-Fonton&nbsp; processes,&nbsp; as&nbsp; well&nbsp; as&nbsp; the&nbsp; determination&nbsp; of&nbsp; achieved efficiency&nbsp; of&nbsp; the&nbsp; appliedprocesses.&nbsp; Also, the degree&nbsp; of mineralization and the identification of degradation products after applied processes were determined. Application&nbsp; of the photo-Fenton process on a real effluent was conducted as well. Based on the obtained results&nbsp; during&nbsp; Fenton&nbsp; process&nbsp; and&nbsp; using&nbsp; both&nbsp; types&nbsp; of&nbsp; catalysts&nbsp; in&nbsp; periods&nbsp; of&nbsp; low&nbsp; and&nbsp; high&nbsp; intensity&nbsp; of&nbsp; radiation, from the aspect of achieving high efficiency of decolorization and smallest iron leaching,&nbsp; it&nbsp; can&nbsp; be&nbsp; concluded&nbsp; that&nbsp; the&nbsp; Fenton&nbsp; process&nbsp; is&nbsp; most effective&nbsp; at&nbsp; pH&nbsp; 3.&nbsp; AlFeB&nbsp; showed&nbsp; greater&nbsp; reactivity even at less used doses of 0.05&nbsp; g, compared to CuOFeB (0.2 g), and the possibility of using&nbsp; less&nbsp; hydrogen&nbsp; peroxide&nbsp; (2.5&nbsp; mM),&nbsp; achieving&nbsp; high&nbsp; efficiency&nbsp; and&nbsp; a&nbsp; high&nbsp; degree&nbsp; of mineralization. Higher intensity of solar radiationallows the reaction to be carried out at higher pH values when using both catalysts during the photo-Fenton process. This is particularly pronounced largest part in the decolorization process using the CuOFeB catalyst has&nbsp; a photolysis of hydrogen peroxide&nbsp; (80%).&nbsp; Contrary&nbsp; to&nbsp; these&nbsp; results,&nbsp; under&nbsp; the&nbsp; same&nbsp; reaction&nbsp; conditions,&nbsp; a&nbsp; higher&nbsp; doses&nbsp; of AlFeB catalyst (0.1 g) is needed at lower pH value&nbsp; of the reaction, and the process efficiency is significantly dependent on the initial concentration of H ₂O₂. The fact that in the preparation of the catalysts bentonite as a natural, abundant, inexpensive material was used and solar&nbsp; radiation as a renewable and alternative source of photons, the above results should&nbsp; be taken into account in the cost-effectiveness&nbsp; analysis&nbsp; of&nbsp; the&nbsp; applied&nbsp; process. Also,&nbsp; the&nbsp; application&nbsp; of&nbsp; advanced&nbsp; oxidation processes is considered as a proposal&nbsp; for the best available technique when it comes to the treatment of&nbsp; wastewater&nbsp; from&nbsp; the&nbsp; textile&nbsp; industry,&nbsp; while&nbsp; as&nbsp; additional&nbsp; new&nbsp; techniques,&nbsp; photooxidation&nbsp; is considered as a candidate and the possibility of their application in the treatment of wastewater in tertiary treatment on semi-industrial systems.</p>

It is a generally agreed internationally that high level nuclear wastes containing long-lived radioactive wastes should be disposed in deep and stable geological formations that are 500-1000 m below ground level. Deep geological disposal is based on the concept of multiple barriers to prevent deep ground-waters, present in almost all rock formations, from rapidly leaching the wastes and transporting radioactivity away from the repository. The multiple barrier system comprises of ‘engineered barriers’ that are constructed in the repository and ‘natural barriers’ in the surrounding geological environment. The engineered barrier components comprise of the vitrified solid waste, canister (to contain the vitrified waste), and a buffer or backfill material (clay or cement) that fills the annular space between the canister and the walls of the hole drilled in the floor of host-rock. The natural barrier is provided by the rocks and soils between the repository and earth’s surface. The canisters containing the hig level waste (HLW) upon placement in DGR need protection against tectonic activities and chemical attack by dissolved elements and from microbes. Densely compacted bentonite is identified suitable for this purpose owing to its large swell potential, low permeability, sufficient bearing capacity and high cation adsorption capacity. In the deep geological repository (DGR) for disposal of high level nuclear wastes, iodine-129 is one of the significant nuclides, owing to its long half-life (half life = 16 million years) and tendency to easily migrate out of the geological repository into the biosphere caused by its high solubility and poor sorption onto most geologic media. Bentonite buffer by virtue of negatively charged basal surface has negligible affinity for retention of iodide anions. Attempts have been made to improve the iodide retention capacity of bentonite by treating the clay with cationic polymers, this however occurs at the cost of reduced swelling ability of bentonite clay. The compacted bentonite employed in deep geological repositories must possess large swell potential to enable it to close fissures and cracks that form on drying of the expansive clay by the heat arising from the high level nuclear waste and thereby close pathways for migration of radionuclides (from breached canister) to the geo-environment. Therefore, it becomes important to identify an additive that enhances the iodide retention ability of the mix without significantly impairing its swelling ability. Based on the strong affinity of silver for iodide ions, the feasibility of mixing silver-kaolinite (termed AgK) clay with bentonite to improve the latter’s iodide sorption capacity and the impact of mixing AgK clay with bentonite on swelling ability of the mix forms one of the the focus of this thesis. Silver-kaolinite clay was prepared by heating 80% kaolinite + 20% silver nitrate mix at 400°C for 30 min, followed by washing (to remove unreacted silver nitrate) and oven-drying the resultant AgK clay. Physical mixing of AgK and bentonite was considered a viable proposition as small additions (10% to 20% on dry mass basis) besides imparting iodide sorption ability was expected to have minor influence on the swelling ability of the mix. As organo-bentonites are known to retain iodide ions, it was considered relevant to compare the iodide removal behaviour of AgK and organo¬bentonite clay. Hexadecylpyridinium-bentonite (termed as HDPy+B) is the organo¬bentonite examined in this thesis and is prepared by treating bentonite with hexadecylpyridinium chloride mono hydrate salt (C21H38ClN.H2O; molecular weight = 358.01). The hexadecylpyridinium chloride mono hydrate salt is a cationic quaternary ammonium compound and has been used by earlier researchers to prepare organo-bentonite for removal of iodide ions from aqueous solutions. The impact of mixing AgK and HDPy+B clays on the iodide retention and swelling behaviour of bentonite is also considered in the thesis. The mass-balance calculations, XRD analysis, X-ray photon emission survey spectrum and EPMA tests performed on kaolinite-silver nitrate mix/AgK/kaolinite specimen indicated that silver occurs as uniform coatings of AgO/Ag2O on kaolinite surface of the AgK specimen. The AgK clay has strong affinity for iodide ions reflected by the large distribution coefficients (Kd) values of 1367 and 293 mL/g at initial iodide concentrations of 750 mg/L and 1000 mg/L. Further, the sorption process was rapid, unaffected by the presence of co-ions, elevated temperature of sorption and was practically irreversible at range of pH conditions. The iodide retention by AgK is attributed to occurrence of hydrolysis and exchange reactions. On contacting the AgK with water, the AgO species hydrolyze to form AgOH; iodide ions are retained by replacing the hydroxyl group of AgOH leading to formation of AgI phase. The adsorption of HDPy+Cl- ions by bentonite occurs by replacement of the native exchangeable cations by HDPy+ ions and adsorption by van der Waals interactions between the organic cations and the clay surface. The adsorbed cationic polymer neutralize the negative charge of the clay surface. Zeta potential measurements of HDPy+B specimen indicated that adsorption of cationic polymer transforms the negatively charged clay particles into positively charged particles that favour anion adsorption. Sorption of iodide ions by HDPy+B specimen exhibits two distinct segments: 1) the iodide sorption increased rapidly at lower iodide concentration (91 mg/L to 475 mg/L) and are retained by Coulombic adsorption to the cationic groups contained in the loops and tails of the adsorbed polymer (primary adsorption sites) and 2) the relatively slower adsorption at higher iodide concentrations (larger than 475 mg/L) is attributed to exchange with chloride ions attached to HDPy+Cl-ion pair (secondary adsorption sites). The Kd values for iodide adsorption vary from 15 mL/g to 184 mL/g at initial iodide concentrations of 91 mg/L to 996 mg/L respectively. Comparing the iodide removal efficiencies of AgK and HDPy+B specimens revealed that the AgK clay exhibited larger iodide removal; further while the iodide removal by AgK specimen was almost instantaneous (complete in < 5 min), iodide removal by HDPy+B specimen was a slow process (18-24 h is needed to attain equilibrium). Likewise, the iodide retention capacity of the 50%B-50%HDPy+B mix (B = bentonite) is substantially smaller than of the 90%B-10%AgK and 80%B¬20%AgK mixes. Cation exchange capacity (CEC) measurements brought out that mixing AgK with bentonite besides imparting an iodide retention capacity essentially retains the large cation exchange capacity of the expansive clay. On the other hand mixing HDPy+B with bentonite imparts a smaller iodide retention capacity to the mix and leads to a notable reduction in the CEC of the expansive clay. Results of oedometer swell tests brought out that dilution of bentonite with 10% and 20% AgK specimen does not impact its swell potential and leads to some (10%) reduction in swell pressure, while dilution with 50% HDPy+B clay leads to notable (58%) reduction in swell potential and swell pressure (21%) underlining the superiority of AgK specimen as additive to bentonite in deep geological repositories. The swell pressure of the compacted 50%B-50%HDPy+B mix is 21% lower than that of the compacted bentonite specimen. Comparatively, dilution of bentonite with 10% and 20% AgK specimen induces 8-10% lower swell pressure in comparison to the undiluted counterpart. Swell pressure results of compacted 80%B-20%HDPy+B mix is not considered as this mix was unable to retain iodide ions. Superposing the field 129I concentration levels on I removal efficiency indicate that use of 90%B-10%AgK mix would suffice to provide 100% iodide removal efficiency and ensure that the swelling characteristics of bentonite is least affected by dilution.